Process of purifying lithium hypochlorite



Patented June 8, 1948 2,443,168: pnoessscrrmmojmrmcn HYPOCHLORITE' liiiomeri'Louiswfiolison Lewiston 'N: Y-., iassi-gnor to' Mathieson Chemical Corporation ia corporation of Virginia Ito-Drawing: Application-August l'li' 191-51 Serial: No. 611,236

Thisinvention relatesto aprocessior the'purification of. lithium: hypochloritemonohydrate, LiGGLI-IzO.

Impurities 1 "removed :fromlithium hypochlorite monohydrate accordingcto the processinclude water; other than the water .molecularly bound in the: lithium hypochlorite rnonohydrate, lithium chlorideand lithium chlorate. One-or allofthese impurities may be present depending-z upon: the method bytwhich the monohydrate has been preparect. The process involves the use of liquid tertiary butyl alcohol as sol-vent in the purification treatment which'may take the form of a simple washing of the impure lithium hypochlorite' monohydratewith the alcohol;

Lfirst conceived of-my process aseone for'the separation of the aboveimpur-ities from anhydrous lithium hypochlorite, i. e. a lithium-hypochlorite-containing' product in which the. water content of the-lithium hypochlorite is not substantially in excessof about=2-3-% on the weighto-f the lithium hypochlorite. However; whenlapplied the processctothe purification of anhydrous lithium-hypochlorite, an alcoholatewas formed which was not clecomposed with.production of lithium hypochlorite by ordinary vaouurni-drying. Thealcohol,..as nearly as I-could ;determine-,=;rep.- resented. about30% of the weight of the-lithium hypochlorite-alcoholcomplex. Although theoalcoholcan be-driven; off to. obtain anhydrous lithium: hypochlorite by employing vacuums and temperatures successful in converting-the monohydrate to anhydrous lithium hypochlorite, such an operation is not commercially practicable-due to the deleterious effect of high concentrationsof tertiary butyl alcohol on the Vacuum pumpmand to the difiiculty encountered in recovering the alcohol from the effluent gas stream. Whilethe' al coholate is-fairly stable in comparison with most organic preparations containing hypochlorite, its handling and storage constltutes'a definite hazard.

I have now unexpectedly discovered that when lithium hypochlorite monohydrate, contaminated with lithium chloride, lithium chlorate-,or water is contacted with tertiary butyl alcohol-under conditions resulting in removal of these impurities, no alcoholate is formed.- In other words, I'have found-thatthe alcohol treatment, althougl winoperable, or-at-least commercially impracticable, in thecase of anhydrous lithium hypochlorite, is Well adapted for the removal of the specifiedcontaminants from the monohydrate.

In .the copendi-n-g application. of Homer L. Robson-and- Edward C; Soule, Serial-No. 475,175,-filed FebruaryB, 1943, new abandoned therev is describ'ed a; method of preparingganhydrens-lithium liypoc-h'l'orite which comprisesrdryingw the-monohydrate ata: temperature: within the range of 20:60 C. at .aipressure lessithan ezthe vapor pressureof-ii water; attithe;particularrteniperature. em p'loyedt'i Occasionally in r the; execution of such procesaldue; usuallygito failure: on the: part of the'roperator toi-properly control tneartemp-erature or'rpressurle or both, partial decomposition of the hy ochioritee with production: oi" chloride and chlorate occursfi" Ai'parti'cuiarly important: appli cati of 'the process ot the preserit inventi'on is iii -the: recovery of i hypoc hlorite values froni'ithese spoiled batli'e's.

Litii'innrhypecmorite monoiaycirate prepared in trie conventionain manner by: clilor'inating an aqul'eoiis sol-fitibr i of lithiu m hydroxide is amenable to pi'irificatien accordihgto Ethe present process. The process is a-lso'applicablei for example; to the purifioat'ion of"li'thiiim hypochlorite monohydrate producedhy reaction of lithium hydi'oxi'd with alkyl-hypo'chlorites-or chlorine monoxide or by'the processes l representing inventionsofnewer-(no. some described 111*- copelndifng applications; S'e'r'ial Nos. 479,778 and 479,779} fildMaii-cl'i lw'l f and b'otli' now' abandoned-.- In 'th e proc'ess of i the" first of said applications; lithium" chic-ride is-'rea'cted With sodium or potassium l'fyp'o'chloritj While in the process 'ofthe'-second,- lithium carbonate or sulfate is reacted"witli an alk-aline earth met-a1 hypochlorite:

If the commercial practice 01 the foregoing rocesses for preparing lithium hypochlorite mon'ohytlrat'e," a' filter" cakeis'obtairied"comprising butyl' alcohol to remove any: remaining amounts of mother liquor present asaneniu'lsion'of'mother liquor andalc'ohol and'toremove-alcohol wet with Water." Finallythe"cake'isaccordedaligfhtdrying under vacuu'nitof separate'a'lcoliol'; Sih'cepn'ly' a minorarnoiint of "alcohol is present," th'er'e'is little adverse efiect ionthevacuuirrpiirrip and economic considerations do not" require" scrubbing of the gasast'reamtoi recover it Thedryingto remove alcoliol'inayb'e f ollowd y; a furtlifdryih'g conducted? unuera vvacuum to: remove th'e"smal1 3 amount of unbound water (2-5%) not separated by the alcohol treatment.

In lieu of pure tertiary butyl alcohol, mixtures thereof with solvents of lower viscosity may be used in the practice of the invention as hereinafter described.

An advantage of the process of the invention resides in the fact that it leaves the monohydrate in a substantially free flowing form in which form it is rapidly and easily converted to anhydrous lithium hypochlorite by the process of application Serial No. 475,175 previously mentioned. In the absence of the alcohol treatment, the amount of unbound water may amount to as much as 30%, and extensive evaporation treatment to remove this water, often accompanied by decomposition of the monohydrate, is therefore necessary. Also, when the drying is by heat alone without prior alcohol treatment, a preliminary grinding operation is usually essential.

When the slurry, supra, contains lithium chloride most, or at least a major portion of the lithium chloride, will be removed in the mother liquor. Ordinarily, when present in the slurry, the lithium chloride will account for about 6-12% of the weight of the solid phase of the cake before alcohol treatment. After the alcohol treatment, the chloride usually accounts for not more than about 0.1% to 4% of the weight of the solid phase of the cake, the exact percentage depending upon the chloride content before alcohol treatment, the care exercised in the re-pulping operation and the manner in which the filtration is carried out. The enumerated factors are also important in connection with removal of chlorate. Removal of chlorate is somewhat more difiicult than removal of chloride because the chlorate is held in an aqueous phase relatively slowly attacked by the alcohol. However, in many instances, I have succeeded in producing a final dry hydrate, by which I mean a lithium hypochlorite monohydrate product essentially free of water not molecularly bound,.having a chlorate content of less than one-fourth that of the slurry from which it was derived. Tertiary butyl alcohol has a high viscosity an this property somewhat retards its removal from the monohydrate preparation by filtering. I have found that theamount of liquid in the cake prior to evaporation treatment to remove alcohol may be reduced by washing the cake, first with a blend of dry tertiary butyl alcohol and another non-reactive solvent of lower viscosity; then with the lower viscosity solvent alone. Two solvents which are particularly suitable are carbon tetrachloride and chloroform. Whereas tertiary butyl alcohol has a viscosity of about three times that of pure water, carbon tetrachloride has a viscosity of slightly less than water and chloroform a viscosity of a little more than half that of water. By washing the butyl alcohol wet cake with a mixture of alcohol and chloroform, for example, or, more preferably, first with the mixture and then with chloroform alone, much less solvent will be left adhering to the lithium hypochlorite monohydrate than where an auxiliary solvent is not used. The cake resulting from this treatment is nearly free flowing, and becomes altogether free flowing upon removal, by evaporation, of the solvent remaining in the cake following the final wash.

The use of an auxiliary solvent, of course, in-

troduces an additional expense. However, I have found, that the bulk of the auxiliary solvent may be recovered by diluting the filtrate with water,

. and used again.

The use of an auxiliary solvent in the manner I described is especiallyadvantageous where 'it is desired to charge the cake directly to a rotary vacuum drier. If the alcohol-Wet cake is not washed with a low viscosity material, before being charged to such a drier, caking will ordinarily occur and this is highly undesirable from the standpoint of the further processing of the monohydrate.

It is to be emphasized that carbon tetrachloride and chloroform are not equivalent to tertiary butyl alcohol in the present process. The passage of a large volume of either of these solvents alone througha filter cake obtained by the illtration of an aqueous slurry of lithium hypochlorite monohydrate will reduce the mother liquor content only about 50% as compared to almost removal in the instance of tertiary butyl alcohol. Re-pulping and re-washing will effect some further reduction, but undesirably large amounts of the Wash liquid are required, most of which short circuits through channels. Moreover, the final cake on drying shows a pronounced tendency to form hard lumps. Carbon tetrachloride and chloroform, as used alone, do not readily wet crystals previously wet with water, and do not easily form an emulsion with water like tertiary butyl alcohol. The properties of tertiary butyl alcohol which render it so well suited for the purification of lithium monohydrate are possessed in only part by its mixtures with carbon tetrachloride and with chloroform.

There are a number of compounds in addition to carbon tetrachloride and chloroform which may be safely mixed with lithium hypochlorite monohydrate and which may be blended with tertiary butyl alcohol to form blends functionally equivalent in the process of the invention to blends prepared with carbon tetrachloride or chloroform. In general, any organic material of lower viscosity than tertiary butyl alcohol and soluble therein which is substantially insoluble in water and non-reactive with respect to lithium hypochlorite monohydrate may be employed in lieu of carbon tetrachloride or chloroform in the practice of the invention. Ortho dichlorobenzene, to cite one example, was employed in a number of experiments with good effect.

Although the initial filter cake -may be repulped with a blend comprising a solvent of lower viscosity than tertiary butyl alcohol, I have found it preferable to re-pulp the initial cake with the pure alcohol. This first re-pulping may be advantageously carried out using a volume of alcohol substantially equivalent to the volume of the cake. In operating in'this fashion, advantage is taken of the high viscosity of the alcohol which aids in mechanically separating adhering masses of crystals which occlude aqueous mother liquor. The re-pulping operation must of course be effected at a temperature above the solidification temperature of the teritary butyl alcohol. This compound exists as a solid at temperatures below 23-25 C. The addition of minor amounts of water lowers this solidification temperature. I

Lithium hypochlorite monohydrate crystallizes in flat plates which may vary in diameter from 1 mm. do-wnto-.01 mm. The small crysdry.compositionawasrmuch.mQrezstableithanthe starting "ferrule" material due-rte :'thelower chlorate. water: and chloride content. I

Table .1

. F )F-ilial .Wssh Crude Damp Hydrate Dry :2 Filtrate Liquor .Bezqccntf Per-cent Gzamsperlitcr Gramsperliter 69. 75209 89.44 7.8- 13.1 i 1:61 3.49 3J2 4.35 v 1.09 1.87' 2.27 .Watenetc 11.02 2&24' 18.3 .414 Avail. Cl-.- 84. 82 81.75 .91. 82 109.38

ploying only vacuum for filtration, it is possible EXAMPLE II to filter, re-pulp, filter, and wash, all in about one half hour, but with small crystals varying from .01 to .02 mm. up to, about nine hours may be required. It is obviously uneconomical to work with small crystals if larger ones can be obtained readily, or if the small crystals. can be simply converted into larger ones. Crystallization of lithium hypochlorite monohydrate from a solution being concentrated under vacuum, the solution having been properly seeded and agitated, ordinarily yields large crystals. Small crystals generally are obtained in the production of lithium hypochlorite monohydrate by the direct chlorination of lithium hydroxide solutions. The size of these crystals may be slightly increased by alternately subjecting the slurry to heating to a temperature of about 40 C; and cooling to a temperature of about C. I generally employ a heating period of less than minutes and a cooling period of several hours with slow stirring and repeat the cycle about six times. In this way filtration time may be reduced as much as one-third.

' ll/iyinvent-ion is further illustrated by the following examples in which parts are byweight:

EXAMPLE I 240 grams of a lithium hypochlorite preparation which had partly decomposed in a drying operation which had as its purpose the production of anhydrous lithium hypochlorite was treated according to the, invention to lower the chlorate and chloride content. This material showed the analysis under crude in .the table below.

There-pulping with tertiary butyl. alcohol. was carried out with one liter of alcohol of 0.814specific gravity containing 5% water. After .flveminutes stirring the mixture was. filtered, the filtration yielding 430 grams..(520 cc.) of filtrate; havinv a specific gravity of 0.828. The cake was then washed with two 150 cc. portions and one 200' cc. portionwoi dry tertiary butyl alcohol, the Washing operationsv yielding 480- grams (580, cc.) ofwash, liquor having a specificgrayity of -828 and 130- grams (158. cc.) of amore dilute wash liquor having a. specific gravity of 0.824;. The strong wash liquor was combined with. the 111- trate and the analysis of the vmixture is given under filtrate below. Analysis of the. weak washliquo-r: is shown under WashLiquor. The washed filter cake-was given-a light vacuum treatment to flash oif alcohol, giving 225 grams of a :fairly free flowing-,slightly damp material having the composition given below as Damp. This material was rapidly dried to: a. composition having the analysis shown under Hydrate. in the table and then the drying was. continued to. site; the-Final dry composition. The final A slurry of lithium hydroxide. was chlorinated to yield a. solution of lithium. hypochlorite and chloride. This was filtered. to .removeimpurities and evaporated under vacuum until the liquid phase contained 17.2% H001 .and 24.0% LiCl and .44% LiCl-Os. The slurryawas then filtered and pressed lightly, obtaining a cake of composition S-linfljable II. 17.8 parts of this cake were re pu-l-ped with 14 parts of dry tertiary butyl: alcohol, and. the resulting slurry filtered. Thefiltrate"separatedintotwolayers. The com.- position. of; the. lower or aqueous layer was L-1 (see table) and that of the .upperlayer -L-2. The cake was then Washed with an additional .22 parts of .teri-tia-ry butyl alcohol, addedin small amounts. A total of 34 parts of filtrate and wash alcohol layer was. obtained, the chloride content of the cake progressively decreasing with each wash. The final cake after light pressing had the, composition 3- This cake was subjectedto vacuum drying to remove alcohol and to slightly dehydrate the monohydrate, the drying yielding a material of compositions-3. From the analyses of the cake S-1 and 0f the original solutionv of the slurry, it will be seen that the cake contained 37% or- 6.6 partsof-mother liquor, and that the aqueous layer obtained on filtration was substantially this amount, showing that the washing procedure removed substantially all the mother liquor. The solid 8-3 was granular and tree flowing, not lumpy, as it would have been if the crystals of the monohydrate had been wet A slurry of lithium "hydroxide was chlorinated to obtain a slurry of lithium hypochlorite monohydrate. The crystalszwere-poor; and were subjected? toalternate heating, and cooling to; improve them. They were filtered by vacuum, obtaining a filter cake of composition S-4. Because of its high chloride content. and. poor crystals this wasoonsidered. a. poor cake for washing tests. 6,9 partsof; this cake were reepulpedwith 32lparts ofdrytertiary butyl alcohol, and. the.- resulting slurry filtered, the. filtration. yielding 51.5. parts of cake, 25 partscf an-aqueous phase of 1.315 specific gravity and'com'position IE3 and. 12.6 'parts composition. The cake was washed'twice with 20 part portions of 50% chloroform-60% butyl alcohol, to obtain 43.2 parts of a cake of composition S5. A small: portion of this cakewas dried to give a monohydrate of composition S-6. As the chloride content was still high, the balance of the cake, about 40 parts, was re-pulped in 25 parts dry tertiarybutyl alcohol and stirred thoroughly to break down aggregates, then filtered and washed twice with 20parts of the half chloroform-half butyl alcohol mixture and once with 15 parts of chloroform. The resulting cake although damp was easily broken up. After flashing off of the chloroform and alcohol, and giving the material a slight drying, 27.0 parts of some unchanged lithium hydroxide monohydrate. wet .with both water and alcohol. The hypochlorite crystals were small. Filtration'of the slurry yielded 754 parts of aqueous phase of 1.31 specific gravity and 1110 parts alcoholic phase having a specific gravity of 0.85. r The alcoholic phase contained 10.7 g. p. l, lithium hypochlorite, and

less than .5 g. p. l. lithium chloride. The aqueous phase contained 38.7% LiOCl. r

The filter cake obtained above was re-pulped with 160 parts of dry tertiary butyl alcohoLandthe resulting mass filtered and washed with an additional 80 parts dry alcohol. This procedure monohydrate of composition 8-7 were obtained.

yielded 52 parts additional aqueous layer, which was assumed to be of the same composition as that obtained in the first filtration. The-cake was then washed with 225 parts of chloroform. 660 parts of chloroform wet cake were obtained, 450 parts of which Were treatedto flash 01f chloroform and alcohol. 308 parts of a lumpy product having an alcohol odor resulted upon the evaporation treatment. To remove the odor of alcohol, the material was ground to 14 mesh fineness and treated under vacuum. Subsequent to Table III s-4 s-s s-e s7 1 L-3 L-4' L-5 Per cent Per cent Per cent Per cent Per cent Per cent LiOOl 0 51.83 11. 0s 13. 92 23. 3 2.14 2.08 LiClO; 23 45 ll 02 trace LiCl. 12. 9 2. 96 4. 92 4. 4 17. 2 3. l8 72 Water, etc 58.1 I Weight 69. 1 43. 2 2* 27 25. 0 12. 6 36 EXAMPLE IV the vacuum treatment the material showed A solution of lithium hypochlorite wasv pre-- pared by agitating 600 parts of LiOI-LI-IzO with 1110 parts water and 1750 parts of 95% tertiary butyl hypochlorite. During the agitation the mixture was maintained at temperatures between C. and C. The aqueous solution was con centrated under vacuum at 40 C. until it contained 47.2% lithium hypochlorite. With further concentration under vacuum a slurry of large crystals of lithium hypochlorite monohydrate was obtained. Thisslurry was cooled to 15 C. and filtered, the filtration yielding 825 parts of filtrate containing 40.68% LiOCl and 1.02% LiCl,

and 500 parts of, cake containing 63.96% LiOCl.

The cake was re pulped with 224 parts of dry tertiary butyl alcohol and filtered. The cake resulting from this filtrationwas washed with 120 parts of a chloroform-35% tertiary butyl alcohol mixture, and then with 150 parts of chloreform. The washed cake (422 parts) contained 54.68% LiOCl. 250 parts of wash liquor having a specific gravity of 0.99 and containing 5.3 grams per liter of LiOCl were obtained. The alcohol and chloroform wereflashed from the cake and the cake given a light drying which gave a monohydrate composition of the following analysis:'

Percent LiOCl 75.14 LiClOa .53

L101 LiOI-l .73

The monohydrate composition was free flowing, and hence easily handled during subsequent further drying. 1

EXAMPLE v I '600' parts of 1.1011320 were stirred with 5o parts Water and 1800 parts of 95% tertiary butyl hypochlorite for several hours, the temperature during the mixing being kept under 30 C. *This produced a slurrycf lithium hypochlorite and 68.25% LiOCl, 39 LiCl and 4.65% LiOH On analysis. Upon further drying a product was obtained analysing:

Per cent LiOCl 67.56 LiC103 .09 LiCl 1.21 LiOI-I 8.98 Water and misc. 22.16

The experiment of Example I illustrates the process of the invention as applied to the treatment of partly decomposed batches of lithium hypochlorites: It will be noticed that in this experlment the alcohol with which the batch was initially pulpedcontained 5% water. This was to prevent the production of a lithium hypochlorite alcoholate which otherwise wouldhave resulted from reaction between the alcohol and hypochlorite in the spoiled batch having less water molecularly associated therewith than is present in lithium hypochlorite monohydrate.

By including the water with the alcohol such hypochlorite became converted to the monohydrate state, in which state lithium hypochlorite is essentially non-reactive with tertiary butyl alcohol. The 5% water was also sufiicient to condry tertiary butyl alcohol in the liquid state and 9 heating the washed cake to drive off residual alcohol and to obtain lithium hypochlorite monohydrate of improved purity,

2. The method of claim 1 in which the viscosity of the tertiary butyl alcohol is reduced by mixing therewith a substantial amount of an organic material of lower viscosity, said material being soluble in the alcohol, substantially insoluble in water and non-reactive with respect to lithium hypochlorite monohydrate.

3. The method of claim 1 in which the viscosity of the tertiary butyl alcohol used in the washing step is reduced by mixing therewith an organic material of lower viscosity, said material being soluble in the alcohol, substantially insoluble in Water and non-reactive with respect to lithium hypochlorite monohydrate.

4. The method of claim 1 in which there is interposed between the washing step and the step of heating the washed cake, a second washing step in which the washing liquid comprises in addition to tertiary butyl alcohol a chlorinated solvent soluble therein having a lower viscosity than tertiary butyl alcohol, said solvent being further characterized in that it is substantially insoluble in water and non-reactive with respect to lithium hypochlorite monohydrate.

5. A process which comprises admixing a 20 Number 10 crude, wet lithium hypochlorite preparation with tertiary butyl alcohol, filtering the mixture, washing the resulting filter cake, first with dry tertiary butyl alcohol, then with a mixture of tertiary butyl alcohol and a solvent of the group consisting of carbon tetrachloride and. chloroform, and finally with a solvent selected from said group in the absence of any tertiary butyl alcohol, and heating the washed cake under conditions resulting in the removal of residual solvent to obtain lithium hypochlorite monohydrate of improved purity.

HOMER LOUIS ROBSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date MacMullin June 14, 1927 Remele Jan. 23, 1934 OTHER REFERENCES Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 11, 1922, page 269, Longmans, Green & Co. London, New York, Toronto. 

